Process of coloring textile materials which comprises cross-linking the textile to awater-soluble dyestuff through a tris aziridinyl phosphine compound



limits the utilization of the class.

United fitatcs Patent The present invention relates to a novel process for thecoloration of textile materials. More particularly it relatesto a process of dyeing and printingtextile materials in bright shades which are characterized by their fastnessto light and to washing.

It is known to color textile materials with (1) substances such as the substantive dyestuffs which are held on the fiber by relatively loose physical forces, i.e., hydrogen bonding, (2) substances which are insolubilized on the fiber such as the vat dyestuffs or azoics, (3) substances which are applied with resins or resin-forming materials and are occluded with the resin as it is formed or I deposited in and on the fiber, and more recently (4) substances which react with the fiber forming a relatively strong chemical bond, i.e., the reactive dyestuffs.

Each of these classes of dyestuffs or coloring methods is deficient in one or more desirable properities which Thus, vat dyestuffs are generallylacking in brilliance and because they are generally applied from strongly alkaline media are limited somewhat as to the fibers to which dyestuffs can be applied. Azoic dyestuffs are not only expensive but also require multistep application procedures. Substantive dyestuffs, although less costly, are often lacking in one or more fastness properties, while reactivedyestuffs are not only expensive but exhaust poorly, and are hence wasteful. Dyestuffs occluded with resins on the fiber give rise to fabrics of inferior handle and of poor physical properties, i.e., reduced wet strength, stiffness, etc.

It is, therefore, a principal object of this invention to I devise a novel process for coloring textile and related materials in bright shades of excellent fastness to light and to washing.

An ancillary object is to devise an effective method for the coloration of cellulosic fibers with non-substantive dyestuffs in shades of excellent fastness to washing.

, 7 Another object is to devise a process of coloring textile materials which is economical to operate and can be carried out in a continuous manner.

A further object is to devise a continuous dyeing process which can be operated simultaneously with one or more finishing operations.

Other objects will be obvious from the following description of our invention.

We have now devised a surprisingly effective, economical process for coloring textile and related materials to produce colorations which are remarkably fast to washing and to light. Our new process comprises impregnating the textile or related material with a solution, dispersion, emulsion, or the like of a mixture or reaction product of a water soluble dyestuff and a tris-aziridinyl compound as hereinafter defined, such as tris-aziridinyl phosphine oxide, preferably in the presence of a catalyst, and heating the impregnated material to firmly fix the dyestuff on the fiber by cross-linking.

The dyestuffs applicable by the process of this invention are those which contain certain reactive hydrogen containing groups which provide a cross-linking site for the aziridinyl compound when activated to bind the dye- ,(acid or alkaline) or by means of heat alone.

stuffs to the textile fiber. Dyestuffs containing one or more of the same or different reactive hydrogen-containing groups can be used. Preferably the dyestuffs should possess little or no affinity for the fiber so that any coloration produced is a result of the chemical reaction,

cross-linking rather than physical absorption or hydrogen bonding.

Aziridinyl compounds are known in the art and have been used, either alone or in conjunction with other resinforming compounds to impart crease-proofing, fireproofing and the like characteristics to textile and allied materials. Such compounds have been polymerized on, or otherwise reacted with the fiber by means of catalysts In our experience, it has been found that the amount of monomeric aziridinyl compound whichis required to provide fireproofiing or crease-proofing or the like properties is far in excess of that amount which suffices to bind certain groups of water soluble dyestuffs to the fiber. Furthermore the fiber undergoes no deterioration of other properties, such as wet strength or wetta-bility, when crosslinked to dyestuffs according to our invention.

Bis-aziridinyl compounds, such as the reaction product of hexamethylene diisocyanate and ethylene imine, when applied to the fiber in the presence or absence of dyestuffs, increase the susceptibility of the fiber to retain chlorine on bleaching the hypoohlorite, which on heating, e.g., ironing, results in loss of strength of the fabric as well as of the dyeing. We have found that textile materials cross-linked to dyestufis in accordance with the process of the present invention demonstrate a reduced susceptibility to chlorine retention on treatment with such bleaching agents.

The novel and useful improvements of the process of our invention are obtainable using an aziridinyl derivative selected from those of the following general formula,

l J Ra Ra 3 wherein X is oxygen or sulfur and R, R R and R are alike or different and are hydrogen or lower hydrocarbon alkyl groups.

As examples of such suitable aziridinyl compounds, the following may be mentioned: Tris-(l-aziridinyl) phosphine oxide Tris-(l-aziridinyl) phosphine sulfide Tris (Z-methyl-l-aziridinyl) phosphine oxide Tris (2-methyl-3-ethyl-l-aziridinyl) phosphine oxide Tris (Z-amyl-l-aziridinyl) phosphine oxide Although these aziridinyl compounds can be activated, that is, caused to crosslink the dyestuff with the fiber by means of heat alone or in the presence of an acid or basic water soluble dyestuffs, preferably acid wool dyestuffs, which contain at least one reactive hydrogen, that is a Patented Sept. 28, 1965 ferred class of dyestuffs therefor.

cobalt, copper, nickel, etc.

I Step 2:

' invention those dyestuffs having hydrogen containingradicals'of the group consisting of amino, imino, carbonamido ,sulfonamido ('SO',NH), and alcoholic'and phenolic hydroxyl are'suitable. 7

Water soluble metallized dyestuffs generally'can be cross'linked particularly well with the textilematerial according to our novel process, and hence constitute a pre- Such dyestuffs, as is well known, are obtained by heating a dyestuff containing chelatable, groups, e.g., 0,0'-dihydroxyazo-, O-hy-.

droxy- O-carboxyazo-, O-hydroxy carboxy, etc. groups,

with a Werner complex forming metal, e.g., chromium,

Such meta-llized water-soluble dyes preferably contain reactive, groups in addition to they hydroxy group present in the chelatable moiety.

The amount'of tris-aziridinyl compounds of the ty described above which can be used to effect cross-linking of the dyestuff and the textile material can be varied over a broad range- The minimumamount is that which is necessary to react with the dyestuff present and'to effect a cross-linking attachment to the fiber. believe, involves a separate aziridinyl moiety for each linkage as indicated by the following reactions which may occur in any order:

Step 1: CHr--CH:

s N .1. 0.1.011 3 N-i-=o ---s the textile goods and then heating to effect a cross-linking reaction chemically bonding'the dyestuff and fiber, as discussed above. However, the invention is not limited This reaction, we

4 groups to react with the textile, e.g., cotton, and thereby chemically bond the dyestuff to'thetextilea Inany event, it is necessary ,toapply the dyestuff and tris-aziridinyl compound to the textile simultaneously. It has been found that stepwise addition of-thedyestuff andcross-linking agent results in a considerably inferior fixation of the dyestuff to the textile. It is also interesting to note that omission of the heating step, during which-most, if not all, of-the cross-linking occurs,- results'in'a colored: fabric from whichthe color can be-removedsubstantially com-- .pletely by the same ;soaping or scouring treatment described in the examples.

We prefer to use an excess over such. theoretical proportion of the tris-aziridinyl compound, and. hence our preferred amount is from 2 to'about 6- moles oftris-aziridinyl compound per mole of dyestuffcontainingiasuitable reactive hydrogen group. The' use' of more than about 6 moles of tris-aziridinyl compound per" mole of. dyestuflf V is generally not required for the cross-linking operation and such excess amounts, while; desirable: in instances where the coloration process is to be combined: with a 'unfelted), films, foils and the like.

crease proofing and/or fireproofing step, are not harmful to the basic process.

The excellent light fastness properties characteristic of dyeing's obtained: by our novel process arez'suprisingsince it iswell known that such properties are often substantial- 1y affected by chemical modification of the dyestuff molecule-as well as by resin finishings applied to textiles.

This new process is applicable. to textile materials derived from naturalor synthetic fibers. which contain a group or groups reactive with 'aziridinyl' compounds. Thus the novel process is effective not only for cotton but also for other cellulosic materials, such as cellulose acetate 1 and regenerated cellulose, polyacrylonitrile, polyesters, polyamides, silk, wool and various blends and mixtures of such natural and synthetic fibers.

The-new process-is adaptable to the coloration (i.e.,

dyeing and/or printing) of not only textile and related materials, e.g., woven fabrics, yarns, fibers (felted or It can be-used to color paper, also.

Our novel process is especially adaptable tov continuous processes for coloring of textile materials, e.g., the padsteam or pad-dry and cure" processes, wherein high speeds and short contact times are generally used. Our preferred procedure, in which anacid (or acid liberating) catalyst is used, accomplishes the cross-linking. in about 3 to 5 minutes, which is generally, adequate for such continuous dyeing. operation.

I When acid catalysts are not used to promote the crosslinking operation during the heating step, 10 to 30 minutes or more'may be required to complete the reaction.

.The following examples illustrate theinvention. Parts and percentages are -by weight andtemperatures are given in degrees centigrade.

EXAMPLE 1 A solution containing 2 parts (approximately 0.0027

mole) of Solantine Turquoise FBL (copper phthalothereto but includes in its broad scope aprocess wherein I the tris-aziridinyl compoundand'dyestuff reactive there- 1 with are fi-rst'reacted in the absence of the textile to produce a dyestuff e.g., I

Dyestufl 1 containing at least one aziridiny'l group,

The dyestuff thus obtained is then applied to the textile and heated (preferably in the presence of an acidic catalyst) to cause one .or both'of the unreacted aziridinyl cyanine containing one ammonium sulfonate and one sulfonamido group), 1 part (0.00578 mole) of tris( l aziridinyl) phosphine oxide (as an byweight solution in ethanol), 192 parts of water, 1 part of dispersing: agent (Triton X-lOO, an alkyl aryl polyether alcohol, Rohm and Haas Co.), 2 parts of tri'ethylamine'and 2 parts of 40% aqueous zincfluoborate was padded on cotton broadcloth (20 parts). The material was passed throughv water (80), scoured by boiling for ten minutes in 1000 parts of. an aqueous 0.2% solution of Triton X-100 and dried at 75 to 80 in a stream of air. v

The amount of dyestuif cross-linked to the cotton fabric linked to the cotton fabric, which was colored a bright greenish blue shade having excellent fa'stness to washing.

EXAMPLES 2 TO 9 The procedure of Example 1 was repeated in a number See footnotes at end of table.

in. this manner was estimated by comparison'of the baked 5 I and unbaked fabric portions and by the visual determina- 9 expenmems (harem the quantPles of crs4mkmg tion of the amount of color bleed in the cold water rinsing agent, water vg 1 .3 g g the paqdmg solu' and scouring steps. This is estimated by diluting an r e s 0 ese experiments are aliquot of the original padding liquor (the dye strength of Own m a e which is known) until the intensity of color of the diluted EXAMPLES 10 TO 69 a 'f the mtenslty of m the combined The procedure described in Example 1 was carried out H1156 and 5Com q m the amount of lf with various dyestuffs while varying the components of Pa Onto the 610th and the amolmi 0f dyestufi In the the padding solution. The results of these experiments rinse and scour llquors, the amount of dyestuflr crossare sh w in Tabl II. linkecllto the fabric can be estimated. Fixation in Examples 2-70 was determined by the 'In'this-example, about of the dyestuif was crosscomparison technique described in Example 1.

' Table I [All quantities are in parts by weight unless otherwise noted] Example. I 2 3 4 5 6 7 8 9 Solantine Turquoise FBL 2 (0.0027 2 (0.0027 2 (0.0027 2 (0.0027 2 (0.0027 1 (0.00133 0.75 (0.001 0 5 (0.000665.

mole). mole). mole) mole). mole) mole). mole). mole). Water 193 01 190 187 184.. 188 1 188.5. APO 0 c. 2 (0.0116 3 (0.0173 6 (0.0347 9 (0.0518 6 (0.0347 6 (0.0347 6 (0.0347 1 mole). mole). mole). mole). mole). mole). mole) Dye Fixation Very poor Good,(70%) Excellent Excellent Excellent Excellent Excellent Excellent (0% (100%). (100%). (100%). (100%). (100%) Trls-(l-azlridinyl) phosphine oxide (85% by weight in ethanol).

7 Table II Parts Parts 1 Example Notes Dyestufl Parts Cross- Parts 5 Parts 8 Dis- Ports Fixation Linking Catalyst Butler persing Water Agent Agent 10 0"-. Benzidine 2,2'-disulio acidltselicyellc acid..- 4 6 1 None 1 188 Excellent. 11 1,5-diamin0-4,8'dihydr0xy anthraquinone-(i- 4 6 1 None 1 188 Good to ex- 4 sodium sulfonate. cellent. 12 H acid- 1 (p-tolyl) amino nephthyl-8- 4 6 1 None 1 188 Excellent.

sodium sulionate. 13 p-Aminosulfo salicyclic acid-91,6 Cleves- N 4 6 2 None 1 137 Very o d,

' (p-salicyl sullo) H acid. 14 z-rzniingrigaphthyl 4,8 disodlum sultonatem- 10 6 2 1. 5 1 180 Excellent.

- o u e. 15 Benzidine 2,2-disullo acldZkN (p-salicyl- '4 6 2 None 1 187 Do. sullo) H acid.

3 -amlno-4 -hydroxybenzene sulionumide-d- 2 12 2 None 1 183 Do.

niaphgzzholib-sodlumsullonate chrome comp ex Bcnzldine 2,2-disultonic acidzkR salt 2 12 2 None 1 183 G003 tot ce en Chromium (2:1) complex of B-amino-thy- 4 6 2 None 1 187 Excellent.

droxy benzene sulfonamlde-vH-ac'id. Nitrol,2,4-acid+H acid (chromed 2:1) 4 6 2 None 1 187 Do. Miitgre 01354 pla'ts dye of Ex. liH-Ld parts 1. 6 10 2 N one 1 133 Do.

0 ye o x. 1 Chromium complex of tl-amino 1,2,4 acld-H 4 10 2 None 1 183 Do.

acid (chromed). I 3-amino4-hydroxybenzene sulfonamide(m- 4 10 2 None 1 183 Do.

emino-phenyl) 3-carboxy-5-pyrazolone (chromed). Cobalt complex of dye of Ex. 22 6 9 3 1. 5 1. 5 279 Do. 2-naphthylamlno-4 8 disulf0nic ocid N-(3,5- 3 6 2 2 l 186 Very good.

his (2-aminoethy1-amino) triazinyi-l) mtoluidine. Cop er phthalocyanlne containing 2sulionic 3 2 B 1 1 187 Excellent.

so (1 and 2-sullonnmide groups. 6-(5-fgnino-2H-benzotriazolyl) 1,2,4-acld- H 6 2 1 1 187 Do.

ac l-emino-2-hydroxy-naphthelenet-sulfo 4 V 6 2 1 187 Do.

acid-v1 (m'suliophenyl) 3-methyl-5 pyrazolone (chromed). Chrorn um complex of 3-amlno-4-hydroxy- 4 10 3 2 1 180 Do.

benzene sultonlc acid-+1 (m-aminophenyD- 3-carboxy-5-pyrazolone.

Chromium com lex oi mono-sulionic acid of 2 6 2 1 1 189 Do.

anthrenllio a d-fll (m-aminophenyl) 3- carboxy-lS-pyrazolone. Copper'comp ex of dye of Ex. 28 2 6 2 1 1 189 Do. Chromium complex of nitro 1,2,4 acid- 8 acid. 2 6 2 l 1 189 Do. Cobalt complex of dye of Ex. 30 2 6 2 1 1 189 Do. Chrome complex of nitro-1,2,4 acid-SS acid.-. 2 6 2 1 1 189 Do. Chromium complex of 3-aminoA-hydroxy-5- 2 6 2 1 1 189 D0.-

nitrobenzenesulionic acid- 88 acid. Cobalt complex of dye of Ex. 32..- 2 6 2 1 1 189 Do. Chromium complex of 3-amino-4-hydroxy-5- 2 6 2 1 1 189 D0. nitrobenzene sulto acid- 8 acid. Cobalt complex of dye of Ex. 35 2 6 2 1 1 189 D0. Chromium complex of dye of Ex. 2 6 2 1 1 189 Do.

group reduced to amino. Cobalt complex of dye of Ex. 28 2 6 2 l 1 189 Do. 39 N-(laminoethyhsullamyl. copper phthelocy- 10 12 4 2 2 371 Do anine monosulfonic ocid.

1 Fabric dyed was cotton twill parts). l Booming solution was 1,000 parts 0.25% aqueous Ivory Snow.

After scouring the tabricwas treated with 0.1 N aqueous hydrochloric acid (pH= 3) ior.30 minutes at 66 and rescoured.

4 To thepedding solution, 20 parts oi 10% a ueous Mothocel (methyl cellulose, Dow Chemical Co.) were added to a orda moroilevel dyeing.

' Parts 40% aqueous Zn fluoborate unless otherwise noted.

I EXAMPLE 70 The following example illustrates the application of Y the present process to textile printing. A mixture of 1 part of the dyestuff of Example 1, 2 parts of Pluronic E 68 00 Y (a'high molecular weight nonionic surfactant prepared by condensing ethylene oxide with a hydrophobic base 'IfOr m ed -byI athe condensation of propylene oxide with propylene glycol; wyandotte. Chemical Corp.) and43.

parts of water was adjusted to a pH of 9by the addition of sodium carbonate 'and SO parts-of 4% aqueous Methocel (methylc'ellulose, Dow Chemical Co.), 3 parts of i tris (l-aziridinyl) phosphine oxide (as an 85 solution.

' in ethyl alcohol), 1 part 40% aqueous zinefluobo rate were added. The mixture was printed on cotton broadcloth and dried, baked and subsequently treated subst'an-' tiallyas describedin Example 1. -In another experiment,

the (foregoing procedure was repeated except that im- '1) ileum was the chromium' Table IIg-Contmued I Y Parts Parts v P Example Notes Dycstufl I Parts Cross-1 I Parts Parts Dis Parts Fixation I Linking Catalyst Bufler parsing Water I Agent I Agent I I 3-umino-4-hydroxy-2-nitrobenzone sullo acid 2 6 2 1 1 188' Do.

-i(2-chloro-5-sultophenyi)3-rnethyl-6-py- Q razgloneneducedl'idia lno benzene sulio I 'xact. I I I 41 6-(5-amino-6-sulfo-2H-benzotriazolyD-l,2,4. I v 2 6 v 2 1 1 13s Do, acid 1(2chloro-5suliophenyl)-3-methyl-5- I Y 1 pyrazolone. Y I v Y 42... .Chromiumcomplexoi6-amino-1,2,4 aeld-v1(2-' 2 6 2 1 1 188 Do. Y fhloro-esulfophenyl)-3-methyl-5-pyrazo- 7 one. Y Cobalt complex of dye of Ex. 42 2 6 2 l 1 188 Do. Dehydrothio p-tolnidinesulioacid-vaceto-ace- I 4 10 3 2 2 179 a Do.

. tylaminobenzene-4-sulio acid. I I I 45 N (3-suiiamylphenyl)-3-nitrosulianilic acid 4 10 3 1' 1 I 181' Gfi'trzex- Y Y Y e on 46 a Same as Ex. 45 4 10 4 1 1' 180 Do. Y 47 Chromium complex of 6(5-amino-2H-benzo tri- 6 12 3 Y 2 2 .176 Excellent. azolyl)1,2,4-acid-+H acid. Y Y Y Cobaltcomplex of6-nitro-1,2.4-acidvSSacid.-- 1 6 2 1 2 I 188' Do. Chrome complexof3-amlno-4-hydroxy-5-nitro- I 4 6 2 2 2 184 Do. I

benzene sulionic acid-'8 acid, redu Cobalt com lex oi dKe oi Ex. 49 '4 6 2 '2 2 I 184 Do. I 1-amino-4(4-aminop enylamino)'anthraqui- 2 I 6 2 -1 2 I 187 Do. I

.no'ne 2,3disulionic acid. I Cobalt complex of 3 -amino-4-hydroxy-5-nltro- 1 6 2 1 2 187 Do. benzene sulionic acid-v8 acid. I I Cobalt complex of 3-aminc-4-hy roxy-b-nitrm 1 6 2. I 1 2 187 Do. I benzene sulionic acid- 88 acid; 54 j Chromiumcomplex oi 3-amino- 4-hydroxyben- 1 6 2 1 2 I 187 vDo. 1 x I 4 zone sulfonic acid H acid. 4 Y I 55-.-; 1,?idialminoi-(4f5-dihydroxy,enthraquin0ne-3,6- 2 '10 B 1 1 188 Very good.

' isu oac 56; Naphthionicacid+-benzidiiie-+henol (treated '4 0 2 2 1 185 Do.

- with benzene sulionyl ehlori e). Y 57 Gammaecidi-p-phenylene. diamineheno l 4 6 2 2 186 D O. (treatedwith benzene sulionyl chlori e). a 68 I 4,4-isopropylidene-dianiline::1(2'chloro-5- 4 6 a 2 2 1 Y 185 I Y D0,. suliophenyl)-3-rnethyl-5-p azolone. v- I v BO Chromium complex'(2;1)'o dyeoi Ex.-26 4 6 2 2 1 185 Excellent. 60 Y Chromium complex;(2.: 1) of 3-amino2hydrox- 4 6 2 2 j 1 I '186 Very good. I ybenz'ene 1,5-disulio acid.-+l(3-aminophev I I v nyl) 3-carboxy-5-pyrazoione. I I Y. r .61 Chromimncomplexizq) oi 3-amino-2-hydroxy- 4 6 2 2 1 185 Do.

, I fi-nitrobenzenesulionlc aeld-vl(3-amino- Y hen l)3-carboxy-5- yrazolone. I -62 C, 0 um complex. 2-1)'oi 2-amino-4-sullo- 2 12 I 8 2 -1 1!] Do.

. v Y benzoic acid-v11(p-aminoplienyl)3-methyl-- I I gg yrazolone. I v 63 .3 no-4-chlorobenzene sulionic acid*1(p- 2 -12 1 1 181 Excellent.

I Y amino-phen D3-mathyI-5-pyrazolone. I M Z-aminonapht alane-o-sulio acid l-hydroxy- 2 10 2 1 182' Very good. 6(m-aminomenzoyl)aminonaphthalene 3- I sulfonic'acid. I v a 65' Z-amino-B-chioro-(i-methyl benzene sullonlc 4 20 6 2 Y 1 4 167' Do. I afid-vl-(m aminophanyl)3carboxy 5-pyraz;; I

oone.. v 66 Cobalt comglex ot3-amino-4 -hydroxybenzene 4 6 2 2 1 185 Do. I s ul ionar rai e-i2-hydroxynaphthalene 3,6-dis oac Y 67 Nickel complex of 3- amino5-chloro-2-hydrox- 4 6 2 2 1 185 Do. I ybenzene sulionic acldv(m-amino-phenyl) a-carboxy-a-pyrazolone.

68 Dyestnfi'oi Ex. 23 4 6 a 2 1 1 166 Excellent. 69 Dyestufl of Ex. 23 4 6 None 1 Y 183 Do.

fixation of dye .in both experiments was rated as excellent, i.e., substantially complete cross-linking of the dyestufi.

I EXAMPLE 71 f I I I (A) A padding liquor was prepared consisting of:

m diazo Z-amino henol-4-sulionic acid con into 1(m-aml hen l internment when... teaches? a... n n O dparts, in; essentially inorganic'salts.

A 6" x15"-strip of polycaproamide cloth was padded j therewith in a conventional three roll padder 0 ratio pregnated mater al was baked without being dried. The 75 at a pressure of 2'00* lbs. on theurolls. picfip we:

was 110.7% and the fixation of dyestutr' was 100%.

which was coloreda bluish-red shade having excellent fastness to washing.

(B) The procedure of part A of this example was re-'- peatedusing asimilar piece of polyhexamethyl'ene adipamide material (Nylon 66) in place of the polycaproamide.. A pick-up of 61.8% was obtained in the padding procedure and by thecross-linkingoperation,.a 100% fixation of the padded dyestuif was-produced.

(C In an analogous manner to that described in part A of this example, polyacrylonitrile (Orlon) textile was padded (111.5% pick-up) anddyed with 100% fixation of the padded dyestutf.

(D)v The procedure of part A of this example was reit peated using a modified polyacrylonitrile (Zephran) fabric-in place of polycaproamide. Pick-up on this fiber From the above examples, it can readily be seen that a remarkably simple, effective andeconomical procedure has been devised for the production of wash fast colorations on textile and related materials. Furthermore, it

' 'can be seen that such colorations may be produced using dyestuifs of superior brightness and lightfastness and preferred shades, which have heretofore been applicable only to materials to which they are substantive.

.We claim:

1. The process of coloring textile and related materials selected from the group consisting of cellulose, cellulose acetate, polyacrylonitrile, polyesters, polyamides, silk, and wool with water soluble dyestuffs non-reactive with the material and having reactive hydrogen containing members selected from the group consisting of alcoholic and phenolic hydroxyls, amino, imino, carbonamido and sulphonamido, which comprises applying to the material a mixture of the 'dyestufi and a cross-linking compound having the general formula where R, R R and R are hydrogens or lower alkyl groups and X is sulphur or oxygen, and heating the material so treated.

2. The process of claim ii in which the dyestuff and cross-linking compound are applied to the material in the presence of an acid catalyst.

3. The process of dyeing textile and related materials containing reactive members selected from the group consisting'of amino and hydroxyl with water soluble dyestuffs non-reactive with the material and having reactive hydrogen containing members selected from the group consisting of alcoholic and phenolic hydroxyls, amino,

imino, carbonamido and sulphonamido, which comprises applying to the material an aqueous mixture of the dyestuff, a cross-linking compound having'the general formula y sented by the structure 4. A composition suitable for coloring cellulosic textile and other related materials to provide washfast colorations, comprising a mixture of a water-soluble dyestutf, non-reactive with the material and having reactive hydrogen containing radicals selected from the group consisting of alcoholic and phenolic hydroxyls, amino, imino, carbonamido and sulphonamido, and a cross-linking compound from the group consisting of tris-aziridinyl phosphine oxide and tris-aziridinyl phosphine sulfide.

5. A colored textile material selected from the group consisting of cellulose, wool, polyamide and silk, in which a water soluble dyestutf, non-reactive with the material and having a reactive-hydrogen containing member selected from the group consisting of alcoholic and phenolic hydroxyls, amino, imino, carbonamido, and sulfonamido,

is chemically bonded to the material by linkages reprewherein M is the textile material;

D is the dyestutf from which reactive hydrogen has been removed;

Z is a member of the group consisting of oxygen and sulfur;

Y is a member of the group consisting of members of the group consisting of hydrogen and lower.

alkyl groups.

6. The product of claim 5 wherein each R is hydrogen. 7. The product of claim 6 wherein the textile material is cellulose.

8. A compound represented by the structural formula 'wherein D is the radical of a water soluble dyestuif having a reactive member selected from the group consisting of alcoholic and phenolic hydroxyls, amino, imino, 'carbonamide and sulfonamido from which member a I reactive hydrogen has been removed; is a member of the group consisting of oxygen and sulfur and R is methylene.

9. The process of dyeing textile and related materials selected from the group consisting of cellulose, cellulose acetate, polyacrylonitrile, polyesters, polyamides, silk and wool with water soluble dyestuffs non-reactive with the material and having reactive hydrogen-containing members selected from the group consisting of alcoholic and phenolic hydroxyls, amino, imino, carbonamido, and sulfonamido which comprises applying to the material an aqueous mixture containing the dyestutf, at least one mol of trisaziridinyl phosphine oxide per mol of dyestutf and an acid catalyst, removing the excess aqueous mixture from the material and heating the material so treated, whereby a nitrogen-carbon bond of at least one aziridinyl ring is cleaved, and a reactive hydrogen of the dyestutf attaches to the nitrogen and the remainder of thedyesmfirmoleculc' attaches;tothe carbon of the cleaved v OTHER REFERENCESv rifl UNITED S'IATES PATENTS I v 5 NORMA)! G, TORCHIN, Primary Examiner.

' :Brodenct aL: Amer. Dyestufi Rcpor t ex f, Jan; 4, 1954, 

1. A PROCESS OF COLORING TEXTILE AND RELATED MATERIALS SELECTED FROM THE GROUP CONSISTING OF CELLULOSE, CELLULOSE ACETATE, POLYACRYLONITRILE, POLYESTERS, POLYAMIDES, SILK, AND WOOL WITH WATER SOLUBLE DYESTUFFS NON-REACTIVE WITH THE MATERIAL AND HAVING REACTIVE HYDROGEN CONTAINING MEMBERS SELECTED FROM THE GROUP CONSISTING OF ALCOHOLIC AND PHENOLIC HYDROXYLS, AMINO, IMINO, CARBANAMIDO AND SULPHONAMIDEO, WHICH COMPRISES APPLYING TO THE MATERIAL A MIXTURE OF THE DYESTUFF AND A CROSS-LINKING COMPOUND HAVING THE GENERAL FORMULA 